Copolymersor thermoplastic elastomers prepared by the anionic polymerization of conjugated dienes and/or styrenes are a unique class of thermoplastics. They differ fundamentally in polymeric structure such as linear copolymers, diblock, triblock, radial, and star polymer structure, and each block structure contributes unique properties to the polymer. These copolymers can be formulated with various other polymers and with a wide range of resins, solvents, and fillers. These copolymers find utility in coatings, adhesives, and sealants.
Copolymers having a functionalized endgroup which have been prepared utilizing anionic polymerization have been disclosed. For example Shepherd et al. in U.S. Pat. No. 5,331,058 discloses a process for anionically polymerizing a conjugated 1,3-diene monomer which consists of contacting the monomer in an inert hydrocarbon solvent with a monofunctional silyl ether initiator to yield a polydiene having a molecular weight of typically 1,000-10,000. It is further disclosed that the reactive ends of the polymer chains may be terminated with a reactive group such as hydroxyl by treating the polymer with ethylene oxide and that subsequent removal of the polymer's relatively unreactive silyl end groups by reaction with tetra-n-butylammoniumfluoride produces a difunctional, chain extendable, hydroxy terminated polydiene.
Handlin, Jr. et al. in U.S. Pat. No. 5,393,843 discloses hydrogenated butadiene polymers having terminal functional groups, such as hydroxyl groups, having a minimum viscosity at any molecular weight when the 1,2 addition is between 30 and 70%.
Bening in U.S. Pat. No. 5,478,899 discloses improved capping of anionic polymers to make functionalized polymers by using alkoxysilyl compounds having protected functional groups, such as acetal groups, as the capping agent. It is further disclosed that the protected functional groups are stable under a variety of conditions and then readily convert to more reactive terminal functional groups useful for making adhesives, sealants, and coatings.
Hydroxy functional poly(ethylene-butylene)is one of the materials that can be prepared by the anionic polymerization of butadiene and subsequent hydrogenation. The hydrogenation process produces a polymer having a saturated olefin backbone, a low viscosity, good water permeability, and good weatherability. The functionality in the poly(ethylene-butylene)polymer can be used in a variety of thermoset and thermoplastic applications. Also, this type of low viscosity, low molecular weight functionalized polymer which contains a polymerizable endgroup is a good macromonomer for use in graft polymerizations.
Silicone polymers also find utility in similar applications such as coatings, adhesives, and sealants where the polymers are often employed in the vulcanization process. Silicone polymers possess favorable properties such as low surface tension, excellent gas permeability, thermal stability, and resistance to ultraviolet light. Since silicone polymers are not miscible with other organic based polymers, distinct phase separation occurs readily for silicone polymers in blends of the two materials, especially when block copolymers or silicone graft copolymers are used. Several copolymers containing an organic polymer segment and a polydimethylsiloxane segment have been synthesized, both by block, star block, and graft polymerization. In block graft copolymerization where for example a polystyrene-polydimethylsiloxanes linear block copolymer is produced, styrene, a lithium initiator, and promoter are anionically polymerized with hexamethylcyclotrisiloxane or coupling of diblock copolymer to form a triblock copolymer.
Hoxmeier, in U.S. Pat. No. 5,276,095 disclose star block copolymers comprised of vinyl aromatic hydrocarbon and/or conjugated diene polymer arms and polydimethylsiloxane arms radiating outwardly from a polyalkenyl aromatic coupling agent core which is produced by first anionically polymerizing a vinyl aromatic hydrocarbon and/or a conjugated diene to produce living polymer arms, reacting the living polymer arms with a polyalkenyl aromatic coupling agent to couple the arms thereto, polymerizing this coupled product with hexamethylcyclotrisiloxane in the presence of a polar promoter, and then terminating the polymerization.
Clemens et al. in U.S. Pat. No. 4,728,571 discloses release coating compositions comprising polysiloxane-grafted copolymer and blends thereof with other polymeric materials which are useful on sheet materials and the backside of adhesive tapes.
U.S. Pat. No. 4,981,903 discloses a composition which can serve as a pressure sensitive or non-pressure sensitive adhesive composition at room temperature comprising a vinyl polymeric backbone with grafted pendant siloxane polymeric moieties.
European Patent Application No. 0412704 discloses hair care compositions comprising 0.1 to 10% of a copolymer having a molecular weight of 10,000 to 1,000,000 which has a vinyl polymeric backbone having grafted to it monovalent siloxane polymeric moieties, the copolymer comprising a silicone containing polymeric monomer and components selected from the group consisting of at least one free radically polymerizable vinyl monomer, and at least one reinforcing monomer copolymerizable with the vinyl monomer and from 0.5 to 99.5% of a carrier suitable for application to hair.
European Patent Application No. 0412707 discloses hair care compositions comprising 0.1 % to 10% of a silicone containing copolymer comprising a silicone-containing macromer having a weight average molecular weight of from 1,000 to 50,000 based on polydimethylsiloxane wand components selected from a lipophilic, low polarity free radically polymerizable vinyl monomer such as methacrylic or acrylic esters, a hydrophilic polar monomer which is copolymerizable with the vinyl monomer such as acrylic acid, dimethylaminoethylmethacrylate, or vinyl pyrrolidone, and mixtures thereof, and from 0.5% to 99.5% of a carrier suitable for application to hair.
Hayama et al. in U.S. Pat. No. 5,166,276 discloses a polymer suitable for use in hair care products comprising a unit of a hydrophilic ethylenically unsaturated monomer such as dimethylaminoethylmethacrylate in a quantity of 15 to 99.9% by weight, a unit of an ethylenically unsaturated monomer having a polysiloxane group in a quantity of 0.1 to 85% by weight, and a unit of an optional hydrophobic unsaturated monomer such as lauryl methacrylate in a quantity of 0 to 84.9% by weight.
Japanese Patent Publication No. 59126478 discloses a coating composition prepared by dissolving silicone graft copolymers prepared by the radical polymerization of a straight chain silicone high molecular weight monomer (I) and radically polymerizable monomer in a solution of film forming resin solvent wherein (I) comprises the reaction product of a living polymer prepared by the anionic polymerization of a cyclic siloxane.
Sojkain U.S. Pat. No. 5,302,379discloses a nail lacquer containing a film forming resin, a plasticizer, and a solvent wherein the film forming resin is a blend of (i) a graft copolymer having a main backbone chain of acrylic ester units and methacrylic ester units, with the main backbone chain having grafted thereto pendant trialkoxysilyl groups and pendant ethylene glycol dimethacrylate groups and (ii) silsesquioxane resin.
Hoxmeier in U.S. Pat. No. 5,281,666 discloses an improvement upon the process for making block copolymers of vinyl aromatic hydrocarbons and/or conjugated dienes, and polydimethylsiloxane by first anionically polymerizing the vinyl aromatic hydrocarbon to make a living polymer block and then adding hexamethylcyclotrisiloxane and a polar promoter to polymerize a polydimethylsiloxane block at the end of the living polymer block. The improvement comprises reacting the living polymer blocks with a crossover reagent to decrease the crossover time from the living polymer block polymerization to the polydimethylsiloxane polymerization.
Hoxmeier in U.S. Pat. No. 5,296,574 discloses a method for producing, in the presence of both monomers, a block copolymer of a polymer block of a vinyl aromatic hydrocarbon (and/or a conjugated diene) and a polydimethylsiloxane which comprises adding a vinyl aromatic hydrocarbon, an organo alkali metal promoter, hexamethylcyclotrisiloxane, and a polar promoter to a solvent, at a temperature of 0 to 60.degree. C., allowing the polymerization of the vinyl aromatic hydrocarbon to proceed until the color of the vinyl aromatic hydrocarbon lithium ion species which is initially produced fades, then raising the temperature to 60 to 120.degree. C. wherein the hexamethylcyclotrisiloxane polymerizes at the end of the polystyrene polymer blocks and then terminating the polymerization.
Unsaturated urea polysiloxanes have been disclosed in combination with copolymerizable comonomers. For example, Mueller et al. in U.S. Pat. No. 5,480,946 discloses styrene functional polysiloxanes which are obtained by the reaction of aminoalkyl functional polysiloxanes with styrene isocyanates. Mueller et al. further disclose that the styrene functional urea polysiloxanes have improved hydrolytic stability and are useful, either alone or in combination with copolymerizable monomers, in oxygen permeable coatings.